Multimodal polymer particles and uses thereof

ABSTRACT

A multimodal polymer particle composition containing two or more populations of polymer particles having a total rubbery weight fraction of less than 90 weight percent is provided. Also disclosed is a process for preparing multimodal polymer particle compositions that can be dried to a powder. Multimodal polymer particle dispersions are disclosed for preparing impact modifiers that can be dried to a powder. Also provided are polymeric compositions having a matrix resin component and impact modifiers prepared from multimodal polymer particles.

BACKGROUND OF THE INVENTION

[0001] This invention relates to multimodal polymer particlecompositions having at least two populations of polymer particles thatare useful as impact modifiers. This invention also relates to plasticsadditive polymer particle dispersions having at least two populations ofpolymer particles that can be formed into a powder. This inventionfurther relates to a process for preparing multimodal polymer particlecompositions having at least two populations of polymer particles thatare useful as impact modifiers. This invention even further relates topolymeric compositions that include a polymeric component and one ormore impact modifiers prepared from multimodal polymer particlecompositions.

[0002] As used herein, the term “multimodal polymer particlecomposition” refers to a composition having at least two populations ofpolymer particles, a “larger mode” and a “smaller mode”, wherein the atleast two populations of polymer particles differ in mean particle sizeby at least 50 percent. Optional additional modes may have mean particlesizes even larger than the “larger mode” as well as smaller than the“small mode”.

[0003] Numerous molded articles and films are manufactured from one ormore of a variety of polymeric resins. Oftentimes, these resins bythemselves are brittle and do not possess suitable impact strengthrequired by the end use for which they are made. To overcome theirshortcomings, resins, especially poly(vinyl chloride), hereinafter“PVC”, are generally blended with plastics additives that improve impactstrength. Such plastics additives are typically known in the industry asimpact modifiers and are often supplied in a powder form.

[0004] Many impact modifiers are based on polymer particles that containa majority amount of a soft rubbery polymer phase (e.g., core)surrounded by a hard polymer phase (e.g., shell), herein referred to as“core-shell” polymer particles. While the rubbery core polymercontributes to the toughening effect of the impact modifier, it isinherently soft and sticky and generally cannot be isolated neatly as adry powder. The hard shell therefore surrounds the sticky core polymerand enables one to isolate the core-shell polymer particles as a drypowder.

[0005] For improving process economics and properties, polymer particlescan be prepared using emulsion polymerization techniques to create abimodal distribution of particle sizes (e.g., a “smaller mode” and a“larger mode”). Such bimodal distributions enable the preparation ofpolymer particle dispersions at high solids (e.g., typically at least 50weight percent) at practicable process viscosities (e.g., typicallybelow about 2000 centipoise, “cPs”).

[0006] Spray drying is an economical, safe and desirable means ofisolating dispersions of polymer particles as free-flowing powders.During this process, an aqueous dispersion of polymer particles isatomized in a chamber containing heated air, water is removed, and thepolymer particles are aggregated into dry powder particles.

[0007] While spray-drying is useful for preparing dry powders fromnon-rubbery (high Tg) polymer particle dispersions that are low inviscosity, there are several problems associated with spray dryingpolymer particle dispersions having high solids, high viscosities, andwhich are composed primarily of a soft, rubbery polymer phase. Theseproblems include: (1) sticking of the particles to the chamber walls ofthe spray dryer; (2) bridging of the particles over conveying linesentrances; and (3) unacceptable powder flow characterized byaggregation, clumping, and flow interruptions.

[0008] It has previously been unrealizable to prepare and dry highsolids rubber-containing multimodal polymer particle dispersions havinga “smaller mode” mean particle size that exceeds 200 nm.

[0009] Canadian Patent 1,256,645 discloses bimodal polymer particledispersions having up to 65 percent solids weight fraction. Thesedispersions, which are prepared by various emulsion polymerizationtechniques, are disclosed to reduce energy requirements and to achievean increase in productivity in the production of powders by spraydrying. While the disclosed polymer particle dispersions are composed inlarge measure of acrylic monomers and have a glass transitiontemperature of at least 45° C., this patent does not address theaforementioned problems associated with spray drying polymer particlescomposed of a majority of a soft, rubbery polymer phase.

[0010] A problem addressed by the present invention is to providemultimodal polymer particle compositions having a soft rubber majorityphase, and having a smaller mode of average particle size of greaterthan 200 nm, which have practicable process viscosities at solids weightfractions of at least 50 weight percent. The term “practicable processviscosities” refers to the ability to prepare polymer particledispersions by emulsion polymerization techniques and to dry (e.g., byspray drying) such dispersions into a powder. We have now discoveredthat certain multimodal polymer particle compositions can be readilyprepared by emulsion polymerization and dried into a powder.

[0011] We have surprisingly discovered that such multimodal polymerparticle compositions are provided as polymer particles that contain twoor more populations (“modes”) of polymer particles that vary in meanparticle size, wherein the mean particle sizes of the two populationsvary by at least 50 percent, and the smaller mode has a mean particlediameter of greater than 200 nm. In addition, we have surprisinglydiscovered that multimodal polymer particle dispersions containing up to95 weight percent total rubbery component, based on total polymerparticle weight, can be readily spray-dried to compact free powders whenthe polymer particles are prepared via a “gradual addition” (as opposedto a “shot monomer addition”) free-radical emulsion polymerizationaddition. We have also discovered that these new multimodal polymerparticles are useful as additives for plastics, and are especiallyuseful as impact modifiers when they contain at least 70 weight percentof a rubbery component.

STATEMENT OF THE INVENTION

[0012] Accordingly, one object of the present invention is to provide amultimodal polymer particle composition, comprising:

[0013] (a) a larger mode of polymer particles, and

[0014] (b) a smaller mode of polymer particles,

[0015] wherein the mean particle size of the larger mode of polymerparticles is at least 50 percent larger than the mean particle size ofthe smaller mode of particles, said smaller mode of polymer particleshaving a mean particle size of greater than 200 nm,

[0016] and wherein the total rubbery weight fraction of the larger andsmaller modes of polymer particles is at most 90 weight percent.

[0017] Another object of the present invention is to provide amultimodal polymer particle dispersion, comprising:

[0018] (a) water, and

[0019] (b) polymer particles, the polymer particles comprising:

[0020] (i) a larger mode of polymer particles, and

[0021] (ii) a smaller mode of polymer particles,

[0022] wherein the mean particle diameter of the larger mode of polymerparticles is at least 50 percent larger than the mean particle diameterof the smaller mode of particles, said smaller mode of polymer particleshaving a mean particle size of greater than 200 nm,

[0023] and wherein the total rubbery weight fraction of the larger andsmaller modes of polymer particles is at most 90 weight percent.

[0024] Yet another object of the present invention is to provide apolymeric composition, comprising:

[0025] (a) a matrix resin component, and

[0026] (b) an impact modifier, the impact modifier comprising,

[0027] (i) a larger mode of polymer particles, and

[0028] (ii) a smaller mode of polymer particles,

[0029] wherein the mean particle diameter of the larger mode of polymerparticles is at least 50 percent larger than the mean particle diameterof the smaller mode of particles, said smaller mode of polymer particleshaving a mean particle size of greater than 200 nm,

[0030] and wherein the total rubbery weight fraction of the larger andsmaller modes of polymer particles is at most 90 weight percent.

[0031] A further object of the present invention is to provide a processfor preparing a multimodal polymer particle composition, comprising thesteps of:

[0032] (I) providing a multimodal polymer particle dispersion, saiddispersion comprising:

[0033] (a) a larger mode of polymer particles, and

[0034] (b) a smaller mode of polymer particles,

[0035] wherein the mean particle size of the larger mode of polymerparticles is at least 50 percent larger than the mean particle size ofthe smaller mode of particles, said smaller mode of polymer particleshaving a mean particle size of greater than 200 nm,

[0036] and wherein the total rubbery weight fraction of the larger andsmaller modes of polymer particles is at most 90 weight percent; and

[0037] (II) drying the multimodal polymer particle dispersion.

[0038] An additional object of the present invention is to provide aprocess for preparing a high-rubber, high-solids multimodal polymerparticle powder, comprising the steps of:

[0039] (I) preparing a high-rubber high-solids multimodal polymerparticle dispersion using a gradual addition polymerization method, saiddispersion comprising:

[0040] (a) a larger mode of polymer particles, and

[0041] (b) a smaller mode of polymer particles,

[0042] wherein the total rubbery weight percentage of the polymerparticles is up to 95 percent, based on total weight of polymerparticles,

[0043] wherein the total solids weight fraction of the dispersion is atleast 50 weight percent,

[0044] and wherein the mean particle size of the larger mode of polymerparticles is at least 50 percent larger than the mean particle size ofthe smaller mode of particles; and

[0045] (II) spray-drying the multimodal polymer particle dispersion to acompaction-free powder.

[0046] These and other objects, as will become apparent from thefollowing disclosure, are achieved by the various embodiments of thepresent invention set out below.

DETAILED DESCRIPTION OF THE INVENTION

[0047] The term “rubbery” used herein denotes the thermodynamic state ofa is polymer above its glass transition temperature.

[0048] The term “units derived from” used herein refers to polymermolecules that are synthesized according to known polymerizationtechniques wherein a polymer contains “units derived from” itsconstituent monomers.

[0049] The term “molecular weight” used herein refers to the weightaverage molecular weight of polymer molecules as determined by the gelpermeation chromatography method.

[0050] The term “graftlinker” used herein refers to multi-functionalmonomers capable of forming multiple covalent bonds between polymermolecules of one type with polymer molecules of another type.

[0051] The term “crosslinker” used herein refers to multi-functionalmonomers capable of forming multiple covalent bonds between polymermolecules of the same type.

[0052] The term “alkyl (meth)acrylate” used herein refers to both alkylacrylate and alkyl methacrylate monomer compounds.

[0053] The term “resin” used herein refers to both thermoplastic resinand thermosetting resins.

[0054] The term “stage” used herein is intended to encompass itsbroadest possible meaning, including the meaning conveyed in prior artsuch as in U.S. Pat. No. 3,793,402; U.S. Pat. No. 3,971,835; U.S. Pat.No. 5,534,594; and U.S. Pat. No. 5,599,854; which offer various meansfor achieving “staged” polymers.

[0055] The term “parts” used herein is intended to mean “parts byweight”. Unless otherwise stated, “total parts by weight” do notnecessarily add to 100.

[0056] The term “weight percent” used herein is intended to mean “partsper hundred by weight” wherein the total parts add to 100.

[0057] The term “weight fraction” used herein is synonymous with “weightpercentage”, when it is evident that the total parts described add to100.

[0058] The term “solids weight fraction” used herein is intended to meanthe weight percentage of the dried residue based on the total weight ofan aqueous particle dispersion that is dried to constant weight.

[0059] The term “particle size” used herein refers to the mean particlesize of a population of particles.

[0060] The term “mode” used herein refers to a particular population ofparticles as in “larger mode” and “smaller mode”.

[0061] The term “core-shell” used herein refers to polymer particleswhich typically have at least one outer polymer phase externallysituated adjacent to an inner polymer phase; the outer phase may besituated as a single phase (shell) or as multiple phases (islands) onthe inner polymer phase (core).

[0062] The term “first population” and “second population” used hereinis for the sake of convenience in identifying two different populationsof polymer particles and has no connotation relating to process order.

[0063] The term “compaction-free” used herein refers to powderycompositions, which are not compactable into a single mass by manuallysqueezing a handful of the powdery composition.

[0064] The term “nm” used herein refers to nanometers.

[0065] All ranges defined herein are inclusive and combinable.

[0066] The Fox Equation as used herein is:

1/Tg=a/Tg(A)+b/Tg(B)+c/Tg(C)+ . . .   [EQUATION 1]

[0067] wherein a, b, c, etc. refer to the weight fraction of monomericcomponents A, B, C, etc. respectively, and Tg(A), Tg(B), Tg(C), etc.refer to the glass transitions for the homopolymers derived frommonomers A, B, C, etc., expressed in degrees Kelvin. Temperature indegrees Celsius (C.) equals temperature in degrees Kelvin (K) plus273.15.

[0068] As will be set out below, the embodiments of this inventionpertain to various aspects of a multimodal polymer particle compositionthat includes a smaller mode having a mean particle size of greater than200 nm and a larger mode having a mean particle size of at least 50percent larger than that of the smaller mode, methods of making suchmultimodal polymer particles, and plastic compositions that include suchmultimodal polymer particles.

[0069] Among other things, this invention resolves at least some of theproblems associated with preparing impact modifier powders frommultimodal polymer particle dispersions having a solids concentration ofat least 50 weight percent, and a rubbery content of up to 90 weightpercent, and a viscosity less than 2000 centipoise. This is accomplishedby the development of novel multimodal polymer particle compositionsthat include a smaller mode having a mean particle size of greater than200 nm and a larger mode having a mean particle size of at least 50percent larger than that of the smaller mode. The novel multimodalpolymer particle compositions can be prepared by emulsion polymerizationtechniques and dried to a powder. Preferably, the novel multimodalpolymer particle compositions are spray dried with a suitable flow aidto reduce powder compaction.

[0070] In one embodiment of the present invention, there is provided anovel multimodal polymer particle composition that includes a largermode of polymer particles and a smaller mode of polymer particles. Inthis embodiment, the total rubbery weight fraction of the larger andsmaller modes of polymer particles is not greater than 90 weightpercent. In this embodiment, the mean particle size of the larger modeof polymer particles is at least 50 percent larger than the meanparticle size of the smaller mode of particles, in which the smallermode of polymer particles has a mean particle size of greater than 200nm.

[0071] In another embodiment of the present invention, there is provideda novel multimodal polymer particle dispersion that includes water andpolymer particles, wherein the polymer particles include at least alarger mode of polymer particles, and a smaller mode of polymerparticles, wherein the total rubbery weight fraction of the larger andsmaller modes of polymer particles is not greater than 90 weightpercent. In this embodiment, the mean particle size of the larger modeof polymer particles is at least 50 percent larger than the meanparticle size of the smaller mode of particles, in which the smallermode of polymer particles has a mean particle size of greater than 200nm. In this embodiment, the size differences among the larger andsmaller modes afford the following advantages over comparable singlepopulation impact modifiers: improved powder flow properties (lesscompaction), possibility of high solids (improved process efficiency),low water content (for advantages in subsequent water removal step),and/or lower in-process viscosity (for improved spray-drying).

[0072] In yet another embodiment of the present invention there isprovided a process for preparing a multimodal polymer particlecomposition wherein the total rubbery weight fraction of the core-shellpolymer particles of the composition is not greater than 90 weightpercent. The process encompassed by this embodiment includes at leastthe following steps. First, a polymer particle dispersion is providedthat includes a larger mode of polymer particles and a smaller mode ofpolymer particles. Then, the polymer particle dispersion is dried. Inthis embodiment, the mean particle size of the larger mode of polymerparticles is at least 50 percent larger than the mean particle size ofthe smaller mode of particles, in which the smaller mode of polymerparticles has a mean particle size of greater than 200 nm.

[0073] In a further embodiment of the present invention, there isprovided a novel polymeric composition which includes a matrix resincomponent and a core-shell impact modifier, wherein the total rubberyweight fraction of the of the impact modifier is no greater than 90weight percent. In this embodiment, the impact modifier is composed ofmultimodal polymer particles that include a larger mode of polymerparticles, and a smaller mode of polymer particles, wherein the meanparticle size of the larger mode of polymer particles is at least 50percent larger than the mean particle size of the smaller mode ofparticles, wherein the particle size of the smaller mode is greater than200 nm. In this case, the size differences among the larger and smallermodes of particles afford the following specific advantages over singlepopulation particles: improved impact properties and reduced dustproblems.

[0074] In these embodiments of the present invention, the dryablemultimodal polymer particle dispersions are optionally spray dried witha flow aid to make compaction-free powders.

[0075] Various means can be used to produce the multimodal polymerparticle dispersions of the present invention which contain multimodalpolymer particles containing no more than 90 weight percent rubberycomponent and having practicable process viscosities. One example of asuitable means for providing such high rubber spray-dryable dispersionsis to employ as part of the polymer particles at least twodifferently-sized populations of polymer particles when the particlesize of the larger mode is at least 50 percent larger than that of thesmaller mode of particles, and the smaller mode of polymer particles hasa mean particle size of greater than 200 nm. In instances where evenlower process viscosities are desirable, the particle size of the largermode of particles is at least 100 percent larger than that of thesecond; more typically at least 200 percent larger than that of thesmaller mode; and even more typically at least 250 percent larger thanthat of the smaller mode.

[0076] Typically, the particle size of the larger mode of particles isat least 350 nm, more typically at least 420 nm, and even more typicallyat least 500 nm. However, problems in impact strength can arise when thelarger mode particle size is too large. Accordingly, when practicingthis invention, the particle size of the larger mode is typically atmost 10,000 nm, more typically at most 1000 nm, and even more typicallyat most 800 nm.

[0077] However, it has also been observed that viscosity problems arisewhen the smaller mode particle size is too small. Accordingly, whenpracticing this invention, the particle size of the smaller mode shouldbe greater than 200 nm; typically at least 210 nm; more typically atleast 230 nm; and even more typically at least 260 nm. These smallermode particle sizes are particularly preferred for preparing multimodalpolymer particles, which are useful as impact modifiers. However, it hasalso been observed that impact problems arise when the smaller modeparticle size is too large. Accordingly, when practicing this inventionfor preparing impact modifiers, the particle size of the smaller modeshould be at most 5,000 nm, typically at most 500 nm, and more typicallyat most 400 nm.

[0078] Although the present invention does not require a particularsolids weight fraction of the dispersion, it has been observed thatthere are certain process and economic advantages associated with havinga polymer concentration greater than 25 weight percent. Accordingly,when practicing this invention, the solids weight fraction of thedispersion is typically at least 25 weight percent; more typically atleast 40 weight percent; and even more typically, at least 50 weightpercent. While the solids weight fraction is typically less than thetheoretical limit of about 87 weight percent, the solids weight fractionis typically less than 80 weight percent, more typically less than 75weight percent, even more typically less than 70 weight percent, andfurther typically less than 65 weight percent.

[0079] Combinations of two polymer populations which vary in particlesize are describable using three main variables: weight percent oflarger population “mode”, particle size of the larger mode, and particlesize of the smaller mode. Diameter Ratio (DR) is equal to the diameterof the larger mode (Dlarge) divided by the diameter of the smaller mode(Dsmall). From a theoretical standpoint, the optimum value of DR formaximizing packing density ranges from 7 to 10.

[0080] In comparison to randomly packed ideal single mode spheres whichhas a packing factor of 0.639, a combination of larger mode and smallermode spheres having a DR of 10 theoretically provides a packing factorof 0.835, while a DR of infinity theoretically provides 0.870.

[0081] While not bound to any particular theory, it is commonly thoughtthat to achieve the maximum packing factor for a combination of largermode and smaller mode polymer particles, the weight percent of thelarger polymer particles should be 73.5 percent. While this theoreticalvalue is for an ideal system for merely maximizing the packing effects,the weight percent of the larger polymer particles may vary depending onproperties provided by the polymer particles.

[0082] Impact modifiers tend to provide better impact strength topolymeric resins as the particle size decreases, thus the weight percentof larger impact modifier polymer particles may be best less than 73.5percent. Accordingly, when practicing the present invention, the weightpercent of the larger mode particles is typically less than 90 percent,more typically less than 85 percent, and even more typically less than80 percent, based on total weight of polymer particles in the multimodaldispersion. In addition, the weight percent of the larger mode particlesis typically greater than 10 percent, more typically greater than 15percent, and even more typically greater than 20 percent, based on totalweight of all polymer particles in the multimodal dispersion. In apreferred embodiment, the weight percent of the larger mode particles isnot in the range of from 40 to 60 weight percent, based on the totalweight of only the smaller mode and larger mode polymer particles in themultimodal dispersion.

[0083] Optional additional modes even smaller than the smaller mode canbe present up to 20 weight percent, typically up to 15 weight percent,more typically up to 10 weight percent, and even more typically up 5weight percent, based on total weight of all polymer particles in themultimodal dispersion.

[0084] In addition, a combination of three or more populations ofpolymer particles that vary in particle size can provide furtherincreases in the packing fraction beyond the theoretical value of 87percent for two populations of polymer particles. Further increases inpacking fraction are expected as the interstitial spaces in thetwo-population system are further filled by particles even smaller thanthe smaller mode.

[0085] In preparing multimodal polymer particle dispersions of thepresent invention, it is desirable that the viscosity of the multimodalpolymer particle dispersion should be no more than 10,000 centipoise,typically no more than 2,000 centipoise, more typically no more than1,750 centipoise, and even more typically no more than 1,500 centipoise.

[0086] In providing powdery impact modifiers of the present invention byspray drying multimodal polymer particle dispersions, it is desirablethat the viscosity of the multimodal polymer particle dispersion shouldbe no more than 2,000 centipoise, typically no more than 1,750centipoise, more typically no more than 1500 centipoise, and even moretypically no more than 1,250 centipoise. These viscosities aredetermined using a Brookfield viscometer with a #3 spindle operating at30 RPM. Polymer particle dispersions that have viscosities greater than2,000 centipoise can be suitably diluted, such as by addition of anaqueous liquid, to reduce the viscosity to 2,000 centipoise or less. Aswell, surfactants may also be added to these polymer particledispersions to improve their shear stability. Accordingly, a high solidsmultimodal polymer particle dispersion provides a much lower viscositythan a high solids polymer particle dispersion having a singlepopulation of comparable polymer particles. Hence, high solidsmultimodal polymer particle dispersions of the present invention aremore readily spray dried than comparable high solids single populationparticle dispersions.

[0087] In one preferred embodiment for providing multimodal polymerparticles at weight percent solids in the range of 60 to 70 weightpercent which are useful for spray drying into multimodal polymerparticle powders that can be used as impact modifiers, it is desirablethat the mean particle size of the smaller mode is in the range of from250 to 300 nm, and the larger mode is in the range of from 550 to 650nm.

[0088] The particles of the impact modifier's core-shell polymerparticles are typically spherically shaped. However, they can have anysuitable shape. Various shapes of core-shell polymer particles can beprepared by processes known in the art of polymer particle technology.Examples of such suitable shapes of particles include: rubbery core/hardshell inhomogeneous particles, hard shell/rubbery core particles,particles having more complex (e.g. three-stage, soft/soft/hard,soft/hard/soft, hard/soft/hard; four-stage soft/hard/soft/hard, etc.)morphologies; ellipsoidal particles having an aspect ratio greater than1:1; raspberry-shaped particles; multi-lobe-shaped particles;dumbbell-shaped particles; agglomerated particles; bilobal particles;and hollow sphere particles.

[0089] The multimodal polymer particle compositions of the presentinvention may also be used as processing aids. Moreover, the multimodalpolymer particle compositions of the present invention that are usefulas impact modifiers may also contain polymer particles that are usefulas processing aids.

[0090] Typical processing aids have polymer compositions exhibiting aglass transition (“Tg”) higher than 25° C. Typical processing aids havepolymer compositions with molecular weights (“MW”) greater than 1million g/mol. More typically, processing aids have molecular weightsgreater than 3 million g/mol. In certain applications, such as preparingPVC foam, processing aids may have molecular weights greater than 6million, and even greater than 10 million. These processing aids mayalso comprise multimodal polymer particles according to the presentinvention.

[0091] Optionally, the multimodal polymer particle compositions of thepresent invention may also include other plastics additives, including:waxes; pigments; opacifiers; fillers; exfoliated clays; toners;antistatic agents; metals; flame retardants; thermal stabilizers;co-stabilizers; antioxidants; cellulosic materials; other impactmodifiers; lubricating processing aids; internal lubricants; externallubricants; oils; rheology modifiers; powder flow aids; melt-flow aids;dispersing aids; UV stabilizers; plasticizers; fillers; opticalmodifiers; surface roughness modifiers; surface chemistry modifiers;adhesion modifiers; surface hardeners; compatibilizers; diffusionbarrier modifiers; stiffeners; flexibilizers; mold release agents;processing modifiers; blowing agents; thermal insulators; thermalconductors; electronic insulators; electronic conductors; biodegradationagents; antistatic agents; internal release agents; coupling agents;flame retardants; smoke-suppressers; anti-drip agents; colorants; andcombinations thereof.

[0092] In one embodiment of the present invention, the aforementionedplastics additives can be added directly to the multimodal polymerparticle dispersions. In other embodiments of the present invention, theaforementioned plastics additives can be subsequently added to the driedpowders of the present invention by various powder processes such as:powder post-blending; co-spray drying; and co-agglomeration.Accordingly, the compositions of the present invention are useful as anytype of plastics additives described herein.

[0093] When practicing this invention for preparing compositions usefulas impact modifiers, the weight percentage of rubbery component of themultimodal polymer particles is greater than 50 weight percent;typically at least 60 weight percent; more typically at least 70 weightpercent; and even more typically at least 80 weight percent.Accordingly, the weight percentage of rubbery component of the particlesis less than 90 weight percent; typically no more than 88 weightpercent, and more typically no more than 85 weight percent.

[0094] Various processes useful for drying the multimodal polymerparticle dispersions include fluidized bed dryers, rotary dryers,continuous or batch tray dryers, flash dryers, and pneumatic conveyingdryers, and preferably spray driers. During the drying step it isimportant to control the drying temperature so that the particles do notfuse among themselves, for example by keeping the temperature of thepolymer particles below the Tg of their hard polymer components (e.g.,outer shells of core-shell polymer particles). If the drying temperatureis too high then the individual polymer particles may fuse together inthe powder particles, which may hinder their subsequent dispersion intothermoplastic matrices. A free-flowing, low-dust plastics additivespowder is achieved when the water content is less than 5%, preferablyless than 3%, most preferably less than 1%.

[0095] For the purposes of preparing multimodal polymer particle powdersof the present invention that are compaction-free, it is desirable todry the multimodal polymer particle dispersions with a flow aid.Accordingly, the weight percentage of flow aid in the compaction-freeimpact modifier powders of the present invention is typically greaterthan 0.5 weight percent; more typically greater than 1 weight percent;and even more typically, greater than 1.5 weight percent. Likewise, theweight percentage of flow aid in the powdery impact modifier istypically no more than 10 weight percent; more typically no more than 8weight percent; and even more typically no more than 5 weight percent.The aforementioned weight percentages are based on the total dry weightof the powder, which includes the polymer particles and the flow aid. Ifmore than one type of flow aid is used to dry the dispersion, then theaforementioned flow aid weight percentages refer to the total weightpercentages of all flow aids used.

[0096] Although higher levels of flow aid may help achieve the desiredimproved drying and flow characteristics, higher amounts of flow aidtypically reduce the impact efficiency. It is therefore desirable toincorporate only the minimum amount of flow aid when a compaction-freepowder is desired. Typically, a compaction-free powder is more desirablethan a powder that is not compaction-free.

[0097] Spray drying can be conducted in any of a variety of designs. Themultimodal polymer particle dispersion is atomized either by a wheel orby a nozzle, and the drying gas can enter from the top or the bottom ofthe atomization chamber. The drying gas is typically heated air ornitrogen to provide a powder temperature that is between the outlettemperature and wet bulb temperature of the drying gas. For acryliccore-shell polymer compositions of the present invention, powdertemperatures are maintained less than 80° C., typically less than 65°C., and more typically less than 55° C. to provide free-flowing powders.Likewise, powder temperatures are maintained greater than 20° C.,typically greater than 30° C., and more typically greater than 40° C. toprovide free-flowing powders at efficient production rates.

[0098] In the spray drying process, optional flow aid may be blown intothe atomization chamber by a separate gas stream or fed into theatomization chamber at such a rate to give the desired weight percentagebased on total polymer particles and flow aid.

[0099] The flow aid is typically an inert particulate material having aparticle size in the range of from 0.005 to 10 microns. Both organic andinorganic flow aids may be used in the present invention. Many suitableflow aids are commercially available. Organic flow aids typicallyinclude hard polymer particles having softening temperature greater thanthat of the spray drying conditions (e.g., polymethyl methacrylate).Flours from plant products such as cellulose fiber, wood and nutshellsmay also be incorporated as flow aids. Suitable inorganic flow aidstypically include a variety of compositions, e.g.: glass beads; metals,minerals such as calcium carbonates, alumina trihydrates, micas,magnesium carbonates, magnesium hydroxide; talcs; clays such as aluminasilicates; ceramics; precipitated amorphous silica; fumed silica;diatomaceous earth, pigments such as titanium dioxide. Both stearic acidcoated and uncoated calcium carbonate flow aids are typically used asflow aids. Various particulate compositions known as “anti-blockingagents” and “fillers” are also useful as flow aids. It is desirable thatthe flow aids are chemically inert and substantially non-reactive withany of the other components commonly found in plastics compositions atprocess conditions.

[0100] The dried powders of the present invention are characterized byhaving a mean particle size of at least 10 microns; typically at least25 microns; more typically at least 50 microns; and even more typicallyat least 100 microns. Spray dried powders of the present invention arecharacterized by having a mean particle size of at most 1000 microns;typically at most 750 microns; more typically at most 500 microns; andeven more typically at most 250 microns. Powder particles larger than1000 microns are typically undesirable, and are subsequently filteredout of the multimodal polymer particle product.

[0101] Spray-dried powders provided by the present invention aretypically characterized as free flowing and low-dust. Typically, thesepowder properties are achieved when the water content is less than 15weight percent, typically less than 10 weight percent, more typicallyless than 5 weight percent, even more typically less than 3 weightpercent, and most typically less than 1 weight percent.

[0102] One variation of the process of the present invention includeshaving optional step(s) for adding one or more other known plasticadditive compositions, in either powder or aqueous form during. Theseother additives can be optionally blended into the composition before,during, or after the final spray-drying step using standard equipmentsuch as high-speed mixers, blenders, kneaders, extruders, and fluidizeddrying beds. Other ingredients typically blended in thermoplasticformulations, such as lubricants, thermal stabilizers, waxes, dyes,pigments, fillers, may each have an aqueous solution, liquid, powdered,or pellet form, and may also be included in the present invention usingthis mixing equipment.

[0103] The two or more populations of the polymer particles used in thepresent invention can be provided for in a number of ways known in theart of polymer science. One method involves blending two or moredistinct polymer particle dispersions, e.g., those prepared by emulsionpolymerization, each having their own particle size; and in-situformation and polymerization of a second particle population in thepresence of a previously polymerized particle population. In anothermethod, free radical emulsion polymerization techniques may be usedwhile providing polymer seeds at different points in the process toprovide for multimodal polymer particles.

[0104] In the processes for preparing the polymer particle dispersionsas provided herein, it is typical that the weight percentage of thepolymer particles is at least 25 weight percent; and more typically atleast 40 weight percent, and even more typically at least 50 weightpercent. Commercially-efficient processes will have a weight percentageof at least 55 weight percent. In the processes for preparing polymerparticle dispersions having viscosities below 10,000 centipoise asprovided herein, it is typical that the weight percentage of the polymerparticles is no more than 80 weight percent; and more typically no morethan 75 weight percent, and even more typically no more than 70 weightpercent, and further typically no more than 65 weight percent.

[0105] Multimodal polymer particles can also be provided by an emulsionpolymerization process in which a second (or subsequent) population ofpolymer particles is created in the presence of a first (or previous)population. The following procedure is illustrative: Starting with atleast one seed polymer particle population in a reaction mixture, addadditional surfactant, and add a portion of a monomer mixture andinitiator to form a second (or subsequent) population of polymerparticles of different size. Next, polymerize the remaining monomers inthe monomer mixture to result in at least two populations of polymerparticles that have mean particle sizes that vary by more than 50percent so that the smaller mode particle size is greater than 200 nm.

[0106] When the multimodal polymer particle dispersion is in an emulsionform, the dispersion may further contain surfactants, emulsifiers,stabilizers, ionic salts, acid or base, oligomeric species, oils, aswell as other plastics additives described herein. In an emulsion form,the polymer particles are typically synthesized by an emulsion processor prepared by an alternative polymerization process and thensubsequently emulsified. More typically, the polymer particles areprepared using emulsion polymerization techniques using variousethylenically unsaturated monomers such as those based on acrylics,dienes, vinyl-halides, vinyl aromatics, ethylene-vinyl acetates, andcombinations thereof

[0107] The multimodal polymer particle dispersions may also be providedusing a process requiring at least two steps of (a) providing an aqueousemulsion polymerization reaction mixture comprising a first populationof polymer particles and a second population of polymer particles; and(b) polymerizing a first group of one or more ethylenically unsaturatedmonomers in the aqueous emulsion polymerization reaction mixture so thatat least one of said populations of polymer particles increases in meanparticle size. Although this process requires that after a portion ofthe first group of one or more ethylenically unsaturated monomers ispolymerized the mean particle sizes of the first and second populationsof polymer particles differ by at least 50 percent, it is typical thatthe mean particle sizes differ by at least 100 percent, and more typicalthat to the mean particle sizes differ by at least 200 percent.

[0108] The multimodal polymer particle dispersion may also be providedusing a process related to the previously described process. Thisrelated process requires at least the two steps of (a) providing anaqueous emulsion polymerization reaction mixture comprising a firstpopulation of polymer particles and a second population of polymerparticles; and (b) polymerizing a first group of one or moreethylenically unsaturated monomers in the aqueous emulsionpolymerization reaction mixture to form a third population of polymerparticles, wherein after a portion of the first group of one or moreethylenically unsaturated monomers is polymerized. Although this processrequires that after a portion of the first group of one or moreethylenically unsaturated monomers is polymerized the mean particlesizes of the first and second populations of polymer particles differ byat least 50 percent, it is typical that the mean particle sizes differby at least 100 percent, more preferable that the mean particle sizesdiffer by 200 percent.

[0109] In the aforementioned processes, the first and second populationsof polymer particles in the aqueous emulsion polymerization reactionmixture of step (a) can be provided by a dispersion combination of thefirst and second populations of polymer particles. In this case, thedispersion combination may be provided by combining separate dispersionsof the first and second populations of polymer particles.

[0110] In the aforementioned processes, the first and second populationsof polymer particles in the aqueous emulsion polymerization reactionmixture of step (a) can also be provided by a dispersion combination ofthe first and second populations of polymer particles. In this case, thedispersion combination may be provided by forming one of the populationsof polymer particles in a dispersion of the other population of polymerparticles.

[0111] In the aforementioned two processes, the first and secondpopulations of polymer particles in the aqueous emulsion polymerizationreaction mixture of step (a) are provided by a dispersion combination ofthe first and second populations of polymer particles, wherein thedispersion combination is provided by forming substantiallysimultaneously the first and second populations of polymer particles ina dispersion.

[0112] In processes where the two populations of polymer particles arepresent, both populations may grow in size during step (b). Likewise, inthe embodiment where a third (or more) population(s) of polymerparticles forms, at least one of the first and second populations ofpolymer particles may grow in size during step (b), however it ispossible that both the first and second populations may grow in sizeduring step (b) during formation of the third population of polymerparticles. This may be accomplished, when after making the second modeusing the surfactant addition, more surfactant is added to make thethird population of polymer particles.

[0113] In another process for providing the multimodal polymer particledispersion used in the present invention, three or more polymer seedparticles can be provided to the reaction mixture. One specificembodiment is where a third polymer seed particle is added to the firsttwo. Multi-populations of polymer particles can also be prepared usingeven more polymer seed particles.

[0114] Accordingly, two-population and three-population multimodalpolymer particle dispersions can be provided wherein at least one of thefirst and second populations of polymer particles substantially does notgrow in size during step (b). This can be provided where one of thepolymer particles is not soluble with monomer, e.g., providing highlycrosslinked polymer particles or selecting polymer types which are notsoluble with monomer. Alternatively, if the rate of polymerization inone seed population is substantially faster than in a second seedpopulation, then (for kinetic reasons) the second population wouldtypically not grow under these conditions.

[0115] As well, in the three-population process, both the first andsecond populations of polymer particles typically do not grow in sizeduring step (b). As discussed above, it is possible to provide twopopulations of polymer particles, which do not grow in size, however theaddition of extra surfactant provides an additional one or more modesthat can grow in size. Alternatively, an independent mode can beprepared using larger swollen particles and smaller emulsion polymerparticles so that independent polymerizations in two different modesresult. Other combinations of growing and non-growing polymer particlescan provide various populations of polymer particles.

[0116] In both of these processes for making a multimodal polymerparticle dispersion having two and three particle populations, theweight fraction of the first population of polymer particles based ontotal polymer particle weight is at least 5 weight percent, typically atleast 10 weight percent, more typically at least 15 weight percent, andeven more typically at least 20 weight percent. Likewise, the weightfraction of the second population of polymer particles based on totalpolymer particle weight is at least 5 weight percent, typically at least10 weight percent, more typically at least 15 weight percent, and evenmore typically at least 20 weight percent. Typically, the smallerpopulation weight fraction is at least 20 weight percent based on totalweight of polymer particles. Typically, the smaller population weightfraction is at most 60 weight percent based on total weight of polymerparticles.

[0117] In the multimodal polymer particle dispersion having either twoor three particle populations, the chemical compositions of the polymerparticles in the larger and smaller modes are substantially the same, ordifferent. They also can be substantially physically the same ordifferent. An example of a physical difference is wherein theethylenically unsaturated monomers form a polymer having different glasstransition temperatures (Tg) according to the Fox equation. Typically,rubbery polymers have a Tg less than 25° C. For providing polymer Tgless than 25° C., typical monomers include: C1 to C18 alkyl acrylatessuch as butyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate; dienemonomers; vinyl acetate monomers; and copolymers thereof. Various otherethylenically unsaturated monomers that can be used in providing polymerTg less than 25° C. are listed in The Polymer Handbook, cited herein.

[0118] In the multimodal polymer particles used in the presentinvention, the ethylenically unsaturated monomers used to form an outerpolymer phase forms a polymer having a Tg according to the Fox equationof at least 25° C., which is typically characteristic of forming hardpolymers. For Tg greater than 25° C., typical monomers include: C1-C4alkyl methacrylates; vinyl aromatic monomers, acrylonitrile monomers,and copolymers thereof. In various embodiments of the present invention,the multimodal polymer particle populations can be prepared with variousethylenically unsaturated monomers in various ratios for the purposes ofpreparing various “hard” versus “soft”, and “brittle” versus “rubbery”polymer phases.

[0119] The processes for making two-, and three-particle populations mayfurther contain a third step (c), which involves polymerizing a secondgroup of one or more ethylenically unsaturated monomers in the presenceof at least the larger and smaller mode of polymer particles to providea polymer adjacent to the surfaces of the polymer particles of thelarger and smaller modes. In this additional step, the second group ofone or more ethylenically unsaturated monomers can be the same as ordifferent from the first group of one or more ethylenically unsaturatedmonomers. In varying the properties of impact modifiers, for example,one typically controls: degree of crosslinking in the core rubber;degree of graft-linking of polymer shells to underlying phases, such asthe core; molecular weight of the polymer shell; and morphology (e.g., ashell or diffusion of particles into the core). In this additional step,the second group of one or more ethylenically unsaturated monomers ispolymerized after at least a portion of the first group of one or moreethylenically unsaturated monomers is polymerized. It is within thepurview of this invention that any combination of cores, shells,interpolymer phases, monomers, crosslinkers, and graftlinkers ispossible for preparing the multimodal polymer particles used in thepresent invention.

[0120] In these embodiments wherein a second group of ethylenicallyunsaturated monomers is polymerized, it is within the purview of thepresent invention that the second group of monomers is polymerized aftersubstantially all of the first group of monomers is polymerized. Thisstep is useful for controlling morphology.

[0121] In preparing a multimodal polymer particle dispersion used in thepresent invention, the first group of monomers forms a rubbery corepolymer and the second group of monomers forms a hard shell polymer.Rubbery core monomers include, for example, alkyl acrylates. The rubberycore monomers may also include 1 percent to 5 percent, based on totalmonomer weight, of one or more crosslinkers. In the case where therubbery monomers include diene monomers, crosslinker may not benecessary as diene monomers tend to self-crosslink. Suchself-crosslinking depends on the reaction conditions and post-reactionconditions as known in the art. The hard shell monomers may contain, asa specific example, methyl methacrylate and styrene.

[0122] Oftentimes, in making core/shell type polymer particles, thesecond group of monomers can be added to the reaction mixture before thefirst group has been completely polymerized so that both monomers fromthe first and second groups are simultaneously present in the reactionmixture. In this situation, while the second group of monomers may notnecessarily copolymerize with the unpolymerized monomers from the firstgroup, it is desirable that at least a portion of the second group ofmonomers copolymerizes with a portion of the unpolymerized monomers fromthe first group of monomers. Likewise, it is desirable that at least aportion of the second group of monomers copolymerizes with substantiallyall of the unpolymerized monomers from the first group of monomers. Thisprocess can be controlled by comparing the reactivity ratios ofmonomers, as known in the art, for preparing separate, alternating,blocky, or random copolymers, as well as combinations thereof.

[0123] With regard to one specific example wherein the multimodalpolymer particle dispersion is in an emulsion form, reactants (e.g.,monomers, initiators, emulsifiers, and optional chain transfer agents,etc.) are typically combined in a reactor with a liquid medium (e.g., anaqueous medium) to form a mixture. Thereafter, and/or simultaneouslytherewith, the mixture is reacted while in the presence of the liquidmedium. The reactants can be added slowly (gradually, as in a semi-batchprocess), over time, continuously, or quickly as a “shot” or“multi-shot” into the reactor. Emulsion polymerization techniques forpreparing polymer particles are typically carried out in a suitablereactor wherein the reactants (monomers, initiators, emulsifiers, pHbuffers, salts, acids, bases, optional chain transfer agents) aresuitably combined and mixed, and reacted in an aqueous medium, andwherein heat may be transferred in to, and away from, the reaction zone.

[0124] In another specific example wherein the multimodal polymerparticle dispersion is in an emulsion form, the process encompasses atleast the following steps. First, an aqueous emulsion polymerizationreaction mixture is provided that includes a first and second populationof polymer particles. These polymer particles as provided for in thereaction mixture are typically referred to by those skilled in the artof emulsion polymerization as “polymer seed particles”, “seedparticles”, or simply “seed”. It is also known to those skilled in theart that polymer particles formed in one step may be further used asseed particles in another step. Then, a first group of one or moreethylenically unsaturated monomers is polymerized in the aqueousemulsion such that the mean particle sizes of the first and secondpopulations of polymer particles differ from each other by at least 50percent. After the polymer particle populations are provided for in areaction mixture, monomers are subsequently added in order to providefor “grow out” of one or both of the polymer seed particle populations.In this embodiment, when both seed particle populations “grow out”, thisgrow-out can occur simultaneously or at different times.

[0125] Methods for polymer seed grow out are useful for preparingpolymer particles having a particle size in the range of from 10 nm to1,000 nm. Typically, monomer and initiator are added to the reactionmixture at conditions to initiate and polymerize monomer as it is addedto the reaction mixture. Typically, the polymer particle size willincrease with increasing seed size. Accordingly, the seed size range canvary from 10 nm to 1,000 nm. In this embodiment, the seed size istypically at least 30 nm, more typically at least 70 nm, and mosttypically at least 100 nm.

[0126] One specific example of providing multimodal polymer particledispersions of the present invention is where a single polymer seed andexcess surfactant is provided into the reaction mixture so that uponaddition of monomer, a second population of polymer particles is formed.In this example, the amount of excess surfactant that is required toform the second population of polymer particles will vary with the typeof surfactant, and conditions of the reaction media to form micelles.Subsequent or simultaneous addition of monomer and initiator into thereaction mixture thereby forms the second population of polymerparticles. This is followed by at least one additional “grow out” stepas described above. Further steps providing additional populations ofseed particles followed by grow-out are also within the scope of thepresent invention.

[0127] Another specific example is providing seeds of two or more sizes,followed by a swelling process. Seeds of two or more sizes can beprovided as previously described. The swelling process typicallyinvolves adding emulsified monomers, or mixtures of monomers to seedparticles present the aqueous reaction media so that the seed particlesswell with monomer prior to forming polymer. The initiator is typicallypresent in the monomer mixture or subsequently added to the reactionmixture. Then, the monomers are polymerized after swelling. By thisprocess, there is no limitation to the upper size of the mean polymersize.

[0128] In a specific example, high-solids multimodal polymer particledispersions containing up to 94 weight percent rubbery component, basedon total weight polymer particles, can be readily spray-dried into acompaction-free powder. In this example, high-solids multimodal polymerparticle dispersions are provided using two rubbery seed particlepopulations in a reaction mixture, to which are gradually added aninitiator, activator, and emulsified monomers. Preferably, emulsifiedmonomers for forming a hard shell polymer are subsequently graduallyadded to the reaction mixture. A thermal initiator is used to carry outthe reaction at temperatures typically greater than 25 C., moretypically greater than 50 C., and even more typically greater than 75 C.The minimum small mode particle size of greater than 200 nm in thisspecific example is readily achieved when the smaller mode seed particlepopulation has a particle size typically at least 50 nm, more typicallyat least 75 nm, and even more typically at least 100 nm. The addition ofpolymerizing monomers onto the seed particles cause the “grow out” ofthese smaller mode particles to greater than 200 nm. In a similarfashion, the requisite larger mode particle size is readily attained byusing a larger mode seed population having a particle size typically atleast 60 nm, more typically at least 100 nm, even more typically atleast 150 nm. In this example, the relative number fractions of theseeds that are used to make the smaller and larger modes correlate tothe desired final smaller mode: larger mode number fractions. Thedesired final smaller mode : larger mode weight fractions is determinedby the relative mass uptakes of each mode. For many of the embodimentsof the present invention, the relative mass uptakes for the smaller andlarger modes will typically be similar so that the final weightfractions of the modes will be similar to the starting weight fractionsof the seed particles.

[0129] Another specific example of forming two populations of polymerseed particles is provided where polymer seed particles of a single modeare partially agglomerated (i.e. “microagglomerated”, as known in theart). In this example, the seed particles agglomerate to differentextents, thereby forming two or more populations of seed particles.Although such microagglomeration steps typically require polymerparticle solids levels less than 40 percent, further swelling andgrow-out steps applied to such microagglomerated seed particles willresult in formation of multimodal polymer particle dispersions havingsolids fractions at least 40 percent.

[0130] Preparing a combination of two polymer particle populations thatdiffer in particle size can be provided using two seeds that vary inparticle size, composition, or a combination of both particle size andcomposition. The final sizes of the particles depend on the startingsize and the starting composition of the seeds. If the seeds are thesame compositions, then they typically grow and/or swell at similarrates of “mass uptake”. The term “mass uptake” refers to the increase inmass of the polymer particles arising from additional monomer and/orpolymer.

[0131] Extent of mass uptake may be estimated according to polymerthermodynamic principles known to those skilled in the art. For example,if the seed compositions are different, then the rate of mass uptakewill generally be different. If the seeds are the same composition butdifferent size, then the larger seed particles will generally remainlarger during mass uptake. As well, increasing the molecular weight ofthe polymer in the seeds generally provides smaller polymer particles.Generally, these and other guidelines for controlling polymer particlesize are estimable via equilibrium swelling calculations according tothe principles of polymer thermodynamics and reaction kinetics as knownto those skilled in the art.

[0132] One or more of these methods may be combined to prepare themultimodal polymer particle dispersions of the present invention. Thoseskilled in the art would be able to readily determine which specificprocess best suits their needs after reading this specification.

[0133] In yet another specific example wherein the multimodal polymerparticle dispersion is in an emulsion form, the process encompasses atleast the following steps. First, an aqueous emulsion polymerizationreaction mixture is provided which includes a first population andsecond population of polymer particles. Then, a first group of one ormore ethylenically unsaturated monomers is polymerized in the aqueousemulsion such that a third population of polymer particles is formed.Formation of the third population can be provided by the addition ofexcess surfactant to form seed particles as described in a previousembodiment, or they can be added separately. The step of swelling and/orgrow-out of the first, second, and/or third population of polymerparticles subsequently follows according to the procedures described ina previous embodiment.

[0134] These various methods for preparing populations of polymerparticles may include one or more of the liquids in the following group:monomers, solvents, non-solvents, chain transfer agents, initiators,surfactants, oils, buffer solutions, stabilizers to prevent polymerparticle coalescence, crosslinkers, graft linkers, aqueous phaseinhibitors for preventing polymerization in the aqueous phase.Accordingly, the multimodal polymer particle dispersions of the presentinvention typically include one or more of these liquids.

[0135] Examples of polymer particle compositions which are within thescope of the present invention include the following polymercompositions: polymers derived from diene, diene/vinyl aromatic, orcrosslinked diene/vinyl aromatic monomers; polymers derived from (C1 toC20) alkyl (meth)acrylates; copolymers derived from (C1 to C20) alkyl(meth)acrylates, (e.g. 2-ethylhexyl acrylate mixed with a butylacrylate); copolymers derived from (C1 to C20) alkyl (meth)acrylateswhich vary in comonomer ratio; copolymers derived from (C1 to C20) alkyl(meth)acrylates which vary in comonomer ratio to provide for differencesin glass transition temperatures, e.g., high Tg (greater than 75 C.)polymer and low Tg polymer and (less than 0 C.); ethylene-vinylacetate(“EVA”) type copolymers; chlorinated polyethylene (“CPE”); polymersderived from olefins; copolymers or blends containing copolymers derivedfrom (C1 to C20) alkyl (meth)acrylates mixed with EVA or chlorinatedpolyethylene (“CPE”) or polyolefins.

[0136] One specific example of different compositions of polymerparticles is when a balance of impact efficiency and UV resistance isdesired. In this case, different compositions can be provided by thefollowing process: emulsion blend of a diene-containing impact modifierwith an acrylic-based impact modifier.

[0137] One specific example of different types of multimodal polymerparticles is where the larger and smaller modes are useful as impactmodifiers and the additional one or more populations are useful asprocessing aids. Combinations of various polymeric additives can bereadily prepared by those skilled in the art.

[0138] The multimodal polymer particle dispersion may also containpolymer particles to balance impact efficiency and UV resistance. Inthis case, different compositions can be provided by the followingprocess: emulsion blend of a diene-derived impact modifier with anacrylic-derived impact modifier. For the purposes of preparing highsolids, one can start with two diene-derived polymer seed particlesvarying in size for preparing the larger and smaller modes of polymerparticles varying at least 50 percent in size. Diene-type monomers aresubsequently polymerized in the presence of these seed particles to formthe larger and smaller modes of diene-derived polymer particles.Additional seed particles are either added to or formed in the reactionmedia containing the larger and smaller modes of diene-derived polymerparticles. Subsequently, polymerization of another type of one or moremonomers, such as a (C1-C20) alkyl (meth)acrylates form on or in theadditional seed particles.

[0139] In the multimodal polymer particle dispersion used in the presentinvention, an additional plastics additive component can be readilyincorporated into the particle dispersion by direct addition,emulsification or suspension by suspending agents in water or a suitablesolvent, and optionally applying shear. The amount of these optionalcomponents can be in the range of from 0 to 100 weight percent;typically from 0 to 20 weight percent; most typically from 0 to 10weight percent of the liquid component. The amount of emulsionstabilizers can be in the range of from 0 to 100 weight percent;typically from 0 to 5 weight percent; most typically from 0.01 to 2weight percent of the liquid component. The amount of defoamers can bein the range of from 0 to 100 weight percent; typically from 0 to 10weight percent; most typically from 0 to 5 weight percent, the weightpercentage being based on the water in the dispersion.

[0140] In one specific embodiment of the process for preparingmultimodal polymer particle dispersions, a dispersion of solid or liquidlubricant particles may also be incorporated in the multimodal polymerparticle dispersion by emulsifying the solid or liquid lubricant inwater or other non-solvent with a surfactant and shear mixing. Thelubricant dispersion is then mixed into the multimodal polymer particledispersion. In a similar fashion, the solid or liquid lubricant may beemulsified in an emulsion, latex, dispersion, or suspension containingone or more other components of the multimodal polymer particledispersion as another embodiment. One specific example is where thelubricant may be emulsified by adding a surfactant and shear mixing in ahigh solids emulsion containing the multimodal polymer particles. In asimilar fashion, because thermal stabilizers are mostly provided asliquids, oils, or solids that are typically non-soluble in water,thermal stabilizers may also be emulsified and added to the multimodalpolymer particle dispersion according to these procedures. Themultimodal polymer particle dispersion may also contain stabilizers andlubricants that can be incorporated into the water component usingorganic solvents. Because stabilizers and lubricants are typicallyinsoluble in water, they may be incorporated into the liquid componentof the multimodal polymer particle dispersion by using organic solventsand/or surfactant to help dissolve or disperse them. In this regard,various solvent/oil/aqueous/surfactant combinations may be employed toprovide dispersions or solutions of one or more additives, such asstabilizers and lubricants, in the water component of the multimodalpolymer particle dispersion.

[0141] Oils which can be used in various embodiments of the presentinvention include, liquid polymers, mineral oils, polymers which have aweight average molecular weight (Mw) of 5000 or less comprisingpolybutene, polydimethylsiloxane, polypropylene, polybutadiene,polyisoprene, preferably the polybutene has a Mw of 300-1500 and thepolydimethylsiloxane has a Mw of 900-3100; alkylacrylates having analkyl group containing 12 or more carbon atoms such as stearyl(meth)acrylate, lauryl (meth)-acrylate; esters containing carboxylicacids or alcohols with 12 or more carbon atoms, for example, methylstearate, ethyl stearate, butyl stearate, stearyl citrate; vegetableoils such as sunflower oil, peanut oil or olive oil; marine oils such ascod liver oil; industrial oils like, castor oil and linseed oil; soybeanoil; palm oil such as coconut oil and animal fats such as tallow.

[0142] In certain embodiments of the present invention, one or more oilscan be added to the compositions for improving the impact strength andprocessability of matrix resin blends. In these embodiments, it ispreferred to incorporate mineral oil in the processes and compositionsof the present invention. Various mineral oils can be used, whichinclude both “light” (e.g., molecular weights less than about 550 g/mol)and “heavy” (e.g., molecular weights greater than about 550 g/mol)mineral oils. If the molecular weight of the mineral oil is too low,then the mineral oil will vaporize too easily. Accordingly, it isdesirable that the flash point of the mineral oil be kept lower than thetemperature at which the composition containing the oil is subsequentlyprocessed. The mineral oil is typically chosen so that it is at leastpartially soluble in the polymer particles of the present invention. Inthese embodiments, the compositions of the present invention may containup to 25 weight percent, typically up to 15 weight percent, and moretypically up to 10 weight percent of a mineral oil, based on totalweight of polymer particles.

[0143] When used as impact modifiers, the compositions of the presentinvention may be used in various ways, including the preparation ofnovel polymeric composition blends that include a matrix resin componentand a core-shell impact modifier component. The blends of the presentinvention contain a matrix resin and an impact modifier powder of thepresent invention, wherein the weight ratio of the impact modifier tothe resin is in the range of from 1:99 to 99:1. These blends can bereadily prepared using blending methods that are known in the art ofplastics processing. For example, the multimodal polymer particles inthe form of powders can be blended with thermoplastic resin powders orpellets and melt processed using an extruder. In addition, themultimodal polymer particles in the form of dispersions can be firstblended with thermoplastic resin powders or pellets in a powder mixingoperation whereby a portion of the water evaporates prior to, orsimultaneously with, melt processing using an extruder.

[0144] The blends of the present invention are especially useful asimpact-modified thermoplastics when the weight ratio of solids portionof the additive to resin is in the range of from 3:97 to 30:70. Theblends of the present invention can also be blended with higher amountsof the powders of the present invention for preparing concentratedpellets of the impact modifiers of the present invention.

[0145] The blends of the present invention may also be formed intopellets by the steps of blending, extruding and pelletizing usingconventional plastics processing equipment. Such pellets may readilycontain the impact modifier powders of the present invention and one ormore resins in the weight ratio of powder to resin can be in the rangeof from 10:90 to 80:20.

[0146] The blends of the present invention have many uses, includingcalendered sheet, thermoformed sheet, injection molded articles,blow-molded articles, extruded articles. When the refractive index ofthe impact modifier is carefully matched to that of transparent resins,the resulting impact modifier is useful in applications requiringtransparency.

[0147] The impact modifiers of the present invention are typicallyblended into poly(vinyl chloride) (“PVC”) and chlorinated PVC (“CPVC”)to improve impact strength. The impact modifiers of the presentinvention are especially useful for manufacturing PVC siding, windowprofiles, and other exterior building products where both impactstrength and weatherability of the PVC product are needed. The impactmodifiers are useful for preparing PVC siding when the impact modifieris present in the PVC formulation in the range of from 4 to 20 parts perhundred resin (“PHR”).

[0148] The impact modifier powders may be blended into many resins otherthan PVC, including thermoplastics based on polymers and copolymers ofalkyl (meth) methacrylate, vinyl aromatics (e.g., styrene), and/or(meth)acrylonitrile, aromatic polyesters such as poly(ethyleneterephthalate) or poly(butylene terephthalate), polycarbonates,polyamides, polyacetals, and polyolefins. The impact modifiers may beadmixed with various blends and alloys of one or more of thesethermoplastic resins. The utility of such blends is varied, but includearticles used in building and construction industries, such as vinylsiding and window profiles, equipment panels and housings, such as forappliances or computers, and automobile parts such as door panels andbumpers. The impact modifiers may also be admixed with thermosettingresins.

EXAMPLES

[0149] The abbreviations listed below are used throughout the examples:MMA = Methyl Methacrylate BA = Butyl Acrylate SLS = Sodium LaurylSulfate ALMA = Allyl Methacrylate t-BHP = tertiary-butyl hydroperoxideSFS = sodium formaldehyde sulfoxylate NaPS = Sodium Persulfate Na2SO4 =Sodium Sulfate DI = deionized wt percent = percent by weight on totalmonomer ppm = parts per million on total monomer nm = nanometers C =degrees Celsius EMM = emulsified monomer mix RPM = revolutions perminute

Example 1

[0150] Heated, deionized water, (1145.37 g), at 88° C. was charged to astainless steel reactor and stirred with an agitator stirrer. Thereactor was sparged with nitrogen gas for 15 minutes and thensubsequently swept with nitrogen. Acetic acid (2.24 g) was added to thereactor. A larger seed latex polymer (214.82 g total latex at 45.06%polymer solids, particle size 330 nm) and a smaller seed latex polymer(1606.16 g total latex at 54.24% polymer solids, particle size 100 nm)were added to the reactor. t-BHP initiator (4.5 grams of 70% t-BHPdissolved in 45 grams of water) and SFS activator initiator (4.6 gramsof 78% SFS dissolved in 115 grams of water) were then added. Thepolymerization was commenced by starting three simultaneous feeds to thereactor. The feed time for all three feeds was 120 minutes. One feedcontained an EMM, 9639 grams total, including EMM additive SLS J, below,consisting of 7335.49 g of BA, 51.71 g of ALMA, 131.13 g of 28% SLS inwater, and 1952.44 g of DI water. A second feed contained t-BHPinitiator solution (2.05 g of 70% t-BHP in 210.26 g DI water). The thirdfeed contained an SFS solution (4.16 grams of 78% SFS dissolved in208.00 g of DI water). The flow rate for the EMM was 80.3 g/minute. Theflow rates for the other feeds (SFS, and t-BHP) were 1.77 g/minute. Thereaction temperature was maintained at 85° C. After 10 minutes of feeds,the EMM SLS (J, 152.96 g total of 28% SLS in water and 15.30 g of DIwater rinse) was added to the EMM feed tank. At the end of the feeds,the EMM feed line was rinsed with 147.74 g of DI water to the reactorand additional SLS (406.26 g total of 28% SLS in water and 40.63 g of DIwater rinse) was added batch-wise to the reactor. t-BHP (2.30 g of 70%t-BHP in 70.77 g DI water) and SFS (1.78 grams of 78% SFS dissolved in71.20 g of DI water), were subsequently added to the reactor as 30minute feeds, each at a rate of 2.44 g/minute. At the end of this rubberstage (core), the sample was sampled for percent total solids. Theactual solids were 59.82% and the theory was 60.68%.

[0151] A second stage polymerization was carried out to form a polymershell on the rubbery core by first lowering the reaction temperature to52° C. The MMA monomer was added as a neat batch-wise charge (1834.06 gMMA, followed by a 91.70 g DI water rinse). The stage II NaPS (1.52 g ofNaPS in 60.80 g DI water) and the stage II SFS (1.52 grams of 78% SFSdissolved in 60.80 g of DI water) were added to the reactor as 30 minutefeeds each at a rate of 2.08 g/minute. The stage II chase t-BHP (1.09 gof 70% t-BHP in 43.43 g DI water) and the chase SFS (0.76 grams of 78%SFS dissolved in 43.43 g of DI water), were added to the reactor as 30minute feeds each at a rate of 1.48 g/minute. At the end of this stage,the reactor mixture was cooled to 40° C. and filtered throughcheesecloth into a 5-gallon bucket. The final viscosity as measured by aBrookfield viscometer using a number 3 spindle at 30 RPM was 390centipoise. The resulting multimodal polymer dispersion contained 63.5weight percent solids fraction (64 weight percent theoretical), rubberycore comprised 82 weight percent of the total polymer particles, largermode: particle size was 590 nm, 70 weight percent of total polymerparticles, smaller mode: particle size was 270 nm, 30 weight percent oftotal polymer particles.

Example 2

[0152] The multimodal polymer particle dispersion of Example 1 wasisolated with a spray dryer. The dispersion was diluted with water toapproximately 30 weight percent solids and subsequently spray dried. Theinlet and outlet temperatures of the spray dryer were 150° C. and 55°C., respectively. In this manner, the water was flashed off and powdercollected (yield of powder: about 98%).

Example 3

[0153] The dispersion of Example 1 was spray dried with a flow aid (2 to3 weight percent based on total solids, Winnofil-S) without priordilution. The conditions for this method were as follows: inlettemperature=113° C., outlet temperature=67° C.; dispersion feedrate=0.52 liters per minute; flow aid feed rate=20 grams per minute;wheel speed=10,000. Powder properties are provided in Table 1.

Example 4

[0154] In this example, mineral oil, (1750 g), (MAPLLC 100 HF SolventNeutral oil, Marathon Ashland Petroleum LLC, Ashland, Ohio), SLS (28%aqueous solution), (624.8 g) and DI water (455 g) were emulsified with ahand held mixer in a 4-liter container. 1.81 kg of emulsified oil wasthen mixed with 27.21 Kg of the multimodal polymer particle dispersionof Example 1, and 3.08 Kg of an acrylic high polymer processing aidpolymer dispersion (54 weight percent solids). The combined mix of themultimodal polymer particle dispersion, mineral oil emulsion andprocessing aid dispersion had a viscosity of about 500 centipoise.

Example 5

[0155] In this example, the combined mix of the multimodal polymerparticle dispersion, mineral oil emulsion and processing aid dispersionaccording to Example 4 was spray-dried to a powder form according to themethod described in Example 3.

Example 6

[0156] In another example, the combined mix of the multimodal polymerparticle dispersion, mineral oil emulsion and processing aid dispersionis spray dried with a flow aid according to the method described inExample 3. The resulting powder has improved flow and compactioncompared to a similar powder composition prepared without the flow aid.Powder properties are provided in Table 1. TABLE 1 Powder PropertiesMoisture Bulk Density Powder Particle Funnel Exam- Content (g/cc) Size(Coulter) Flow ple % Loose Tapped Mean Median Span seconds Ex. 3 0.60.580 0.678 93 104 1.09 12.0 Ex. 6 0.6 0.554 0.620 90 101 1.2 15-20

Example 7

[0157] The powders of Examples 3 and 6 (4.5 PHR) were used as impactmodifiers and blended with PVC resin according to the following PVCsiding substrate masterbatch formulation: Component Parts by weight(PHR) Resin, PVC (Geon 103, K = 68): 100 Thermal Stabilizer, ADVASTABTM-181 0.9 (Rohm and Haas) Lubricant, Wax-165 (Allied Chemical) 0.9Lubricant, Calcium Stearate 1.4 Lubricant, PE Wax 0.1 Filler, calciumcarbonate (Omya UFT) 10 Pigment, TiO2 1.0 Processing Aid, PARALOIDK-120N 0.5 (Rohm and Haas) Impact Modifier Powder 4.5

[0158] The PVC masterbatch was melt-extruded using a CM-35 extruder(Cincinnati Milacron, Ohio) into sheet having a thickness of 1.2 mm.Impact performance of the sheets was tested by the drop-dart method (3.6kg dart dropped from 62.2 cm height, ASTM Method D4226). The sheetsprepared using each of the multimodal particle powders of Example 1 andExample gave a drop-dart result of 13 passes out of 24 tested. Here,“pass” means did not tear or break. In comparison, a sheet preparedwithout the multimodal polymer powders results in zero, or at best one,“pass” out of 24 tested. As a result, the multimodal polymer particlepowders of the present invention are useful as impact modifiers forplastic resins.

We claim:
 1. A multimodal polymer particle composition, comprising: (a)a larger mode of polymer particles, and (b) a smaller mode of polymerparticles, wherein the mean particle size of the larger mode of polymerparticles is at least 50 percent larger than the mean particle size ofthe smaller mode of particles, said smaller mode of polymer particleshaving a mean particle size of greater than 200 nm, and wherein thetotal rubbery weight fraction of the larger and smaller modes of polymerparticles is at most 90 weight percent.
 2. A multimodal polymer particlecomposition as recited in claim 1, further comprising up to 20 weightpercent, based on total weight of polymer particles in the composition,of a third population of polymer particles having a mean particle sizesmaller than 200 nm.
 3. A multimodal polymer particle composition asrecited in claim 1, wherein the total rubbery weight fraction of thelarger and smaller modes of polymer particles is at least 70 weightpercent.
 4. A multimodal polymer particle composition as recited inclaim 1, further comprising at least one oil.
 5. A multimodal polymerparticle composition as recited in claim 1, wherein the composition isin the form of a powder.
 6. A multimodal polymer particle dispersion,comprising: (a) water, and (b) polymer particles, said polymer particlescomprising: (i) a larger mode of polymer particles, and (ii) a smallermode of polymer particles, wherein the mean particle diameter of thelarger mode of polymer particles is at least 50 percent larger than themean particle diameter of the smaller mode of particles, said smallermode of polymer particles having a mean particle size of greater than200 nm, and wherein the total rubbery weight fraction of the larger andsmaller modes of polymer particles is at most 90 weight percent.
 7. Amultimodal polymer particle dispersion as recited in claim 6, whereinthe dispersion has a viscosity up to 2000 centipoise.
 8. A multimodalpolymer particle dispersion as recited in claim 6, further comprising atleast one oil.
 9. A multimodal polymer particle dispersion as recited inclaim 6, further comprising up to 20 weight percent, based on totalweight of polymer particles in the composition, of a third population ofpolymer particles having a mean particle size smaller than 200 nm.
 10. Apolymeric composition, comprising: (a) a matrix resin component, and (b)an impact modifier, the impact modifier comprising, (i) a larger mode ofpolymer particles, and (ii) a smaller mode of polymer particles, whereinthe mean particle diameter of the larger mode of polymer particles is atleast 50 percent larger than the mean particle diameter of the smallermode of particles, said smaller mode of polymer particles having a meanparticle size of greater than 200 nm, and wherein the total rubberyweight fraction of the larger and smaller modes of polymer particles isat most 90 weight percent.